CN110004293A - The stanniferous processing method for decomposing slag - Google Patents

The stanniferous processing method for decomposing slag Download PDF

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Publication number
CN110004293A
CN110004293A CN201910159635.9A CN201910159635A CN110004293A CN 110004293 A CN110004293 A CN 110004293A CN 201910159635 A CN201910159635 A CN 201910159635A CN 110004293 A CN110004293 A CN 110004293A
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mother liquor
stanniferous
slag
iron
added
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CN110004293B (en
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霍广生
郭磊
易新涛
蒲海鹏
刘辉
马顺
曾璐琦
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Central South University
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Central South University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/46—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/02—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B25/00—Obtaining tin
    • C22B25/04—Obtaining tin by wet processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B25/00—Obtaining tin
    • C22B25/06—Obtaining tin from scrap, especially tin scrap
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C22B7/007—Wet processes by acid leaching
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Geology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

The present invention relates to a kind of stanniferous processing methods for decomposing slag, comprising steps of Step 1: by stanniferous decomposition slag and initial H+Concentration is that the dilute hydrochloric acid solution of 3.0mol/L-5.0mol/L is stirred to react in confined conditions, and acid dissolution slag and acid dissolution mother liquor is obtained by filtration；Step 2: H is added into the acid dissolution mother liquor2O2, CaCO is added3, CaO and Ca (OH)2One of or a variety of pH by acid dissolution mother liquor be adjusted to 3.0-4.0, obtain arsenic scum and arsenic removal mother liquor；Step 3: continuously adding H into arsenic removal mother liquor2O2, CaCO is used later3And/or Ca (OH)2The pH of arsenic removal mother liquor is adjusted to 5.0-6.0, obtains hydroxide scum and except iron mother liquor；Step 4: making the calcium chloride in solution be converted into calcium sulfate precipitation and HCl solution to except sulfuric acid is added in iron mother liquor.The present invention not only increases the grade of tin in stanniferous decomposition slag, and by slag most of calcium and iron be separately converted to calcium sulfate and iron hydroxide, and realize being recycled for a long time for hydrochloric acid solution, achieved the purpose that recycling and clean manufacturing.

Description

The stanniferous processing method for decomposing slag
Technical field
The present invention relates to the processing technology fields for decomposing slag, more particularly to a kind of stanniferous processing method for decomposing slag.
Background technique
Tungsten tin mine is a kind of more typical multi-metal oxygen mine, wherein general stanniferous 5-30%, containing WO35-40%, wherein Tin mainly exists with the state of stannic oxide, and tungsten exists mostly with artificial schellite or iron tungstate or manganese tungstate state, in addition to this also Contain silicate, calcirm-fluoride and a small amount of arsenic-containing ores.For tungsten tin mine, general tungsten therein and tin to be separated can be using choosings The method of mine carries out just point, but inferior separating effect and metal recovery rate it is low.And first tungsten therein is extracted by the method for metallurgy Out, then good separating effect can be obtained, is sintered water logging generally by sodium carbonate high pressure lixiviation process either sodium carbonate Method selectively extracts tungsten, and tin then remaines in the slag after extracting tungsten.
For the decomposition slag obtained after separation and Extraction tungsten, if wherein it is stanniferous be greater than 30% if be used directly for tin also Former smelting process produces metallic tin, lower for Theil indices to generally require the further grade of enrichment raising tin or pass through fuming Technique, which is directly volatilized, recycles tin therein.The method that enrichment improves tin grade in above-mentioned decomposition slag can generally pass through the hands such as ore dressing Section, but decompose that the physics of slag, chemical property are complicated due to stanniferous, the effect of beneficiation enrichment is limited and the rate of recovery of tin is low.
Summary of the invention
The invention solves the stanniferous decomposition slags how to obtain tungsten tin mine after soda decomposition to carry out minimizing processing It to improve tin grade, while realizing the resource utilization of the elements such as calcium in slag, iron, and realizes recycling for treatment process waste water The technical issues of.
In order to solve the above technical problems, the invention proposes a kind of stanniferous processing methods for decomposing slag.
A kind of stanniferous processing method for decomposing slag, comprising the following steps:
Step 1: acid dissolution:
By the stanniferous decomposition slag and initial H+Concentration is the dilute hydrochloric acid solution of 3.0mol/L-5.0mol/L in confined condition Under be stirred to react, acid dissolution slag and acid dissolution mother liquor are obtained by filtration later；
Step 2: precipitating arsenic removal:
H is added into the acid dissolution mother liquor that step 1 obtains2O2, CaCO is added later3, CaO and Ca (OH)2In One or more pH by the acid dissolution mother liquor are adjusted to 3.0-4.0, obtain arsenic scum and arsenic removal mother liquor；
Step 3: precipitating removes iron:
H is continuously added into the arsenic removal mother liquor that step 2 obtains2O2, CaCO is used later3And/or Ca (OH)2It will be described The pH of arsenic removal mother liquor is adjusted to 5.0-6.0, obtains hydroxide scum and except iron mother liquor；
Step 4: hydrochloric acid transformation tissue culture:
To step 3 obtain described in except sulfuric acid is added in iron mother liquor, so that the calcium chloride in solution is converted into calcium sulfate precipitation And HCl solution.
Preferably, in step 1, the stanniferous decomposition slag and the initial H+Concentration is 3.0mol/L-5.0mol/L's The solid-to-liquid ratio of dilute hydrochloric acid solution is to be stirred to react described in 1:3-8 is carried out.
Preferably, in step 1, the time being stirred to react is 2.0-4.0h.
Preferably, it in step 1, is stirred to react described in progress at 80-95 DEG C.
Preferably, in step 2, the H2O2Additional amount according to by the iron in the acid dissolution mother liquor by Fe2+Oxidation For Fe3+0.05-0.1 times of required theoretical amount is added.
Preferably, in step 3, the H2O2Additional amount according to by the iron in the arsenic removal mother liquor all by Fe2+Oxygen Turn to Fe3+0.8-1.0 times of required theoretical amount is added.
Preferably, further include the washing stanniferous sodium decomposed in slag before step 1: will the stanniferous decomposition slag and Water is mixed and added into the pH to 6.5-7.5 of hydrochloric acid conditioning solution, stirs to get sodium chloride washing lotion later and except containing described in after sodium Tin decomposes slag.
Preferably, in step 1, when in the acid dissolution mother liquor contain Na+It further include removing the acid when > 40.0g/L It dissolves the sodium ion of mother liquor: the acid dissolution mother liquid evaporation is concentrated into CaCl2Concentration is 400-600g/L, is cooled to 20-40 It is filtered to remove the sodium chloride crystal that condensing crystallizing is precipitated to obtain filtrate after DEG C, is later supplemented to the volume of the filtrate with water The volume of the acid dissolution mother liquor before evaporation and concentration, at this time Na in solution+Concentration be down to 1.0-10.0g/L.
Preferably, in step 4, to described except the sulfuric acid being added in iron mother liquor is the concentrated sulfuric acid, the concentrated sulfuric acid dosage is pressed The HCl that conversion obtains 3.0mol/L-5.0mol/L calculates and is 1.0-1.1 times of required theoretical amount.
Preferably, it in step 4, is removed in iron mother liquor before addition sulfuric acid to described, further includes to described except in iron mother liquor Add calcium chloride, wherein the dosage of calcium chloride obtains the HCl of 3.0mol/L-5.0mol/L by conversion and makes excess 10- in solution 20g/L Ca2+It is supplemented.
The beneficial effect of the present invention compared with the prior art includes:
By by stanniferous decomposition slag and initial H+Concentration is the dilute hydrochloric acid solution of 3.0mol/L-5.0mol/L in confined condition Under be stirred to react, be obtained by filtration acid dissolution slag and acid dissolution mother liquor, it is molten that stanniferous iron, calcium and the arsenic decomposed in slag enters acid In hydrolysis mother liquor, wherein being stirred to react in confined conditions farthest makes the iron in acid dissolution mother liquor with Fe2+Form In the presence of the quality of obtained acid dissolution slag can reduce to the 20-60% of the quality of the stanniferous decomposition slag before acid dissolution processing, improve The grade of tin in stanniferous decomposition slag continues that H is added into the acid dissolution mother liquor2O2, CaCO is added later3, CaO and Ca (OH)2One of or a variety of pH by the acid dissolution mother liquor be adjusted to 3.0-4.0, control the Fe in solution2+It is oxidized to Fe3+'s Amount makes least a portion of iron precipitate with hydroxide Iron activiation, while this least a portion of iron can be by most of arsenic in solution Co-precipitation, to remove the arsenic in acid dissolution mother liquor, continues to continuously add H into the arsenic removal mother liquor that step 2 obtains2O2, CaCO is used later3And/or Ca (OH)2The pH of the arsenic removal mother liquor is adjusted to 5.0-6.0, obtain hydroxide scum and removes iron mother liquor, Most of iron in solution is removed as ferric hydroxide, continues to make in solution to described except sulfuric acid is added in iron mother liquor Calcium chloride be converted into calcium sulfate precipitation and HCl solution, except the calcium in iron mother liquor is converted into calcium sulfate, furthermore except iron mother liquor convert For HCl solution, which can go in step 1 and recycle.
By carrying out acid dissolution in confined conditions farthest to make the iron in solution with Fe2+Form exist, so Pass through control Fe again afterwards2+It is oxidized to Fe3+Amount, be co-precipitated small part iron with the arsenic in solution, to not only protect Card has purified the arsenic in solution, and also greatly reduces the amount of arsenic scum.It is useless by what is generated in acid dissolution treatment process simultaneously The hydrochloric acid solution that liquid is converted into byproduct calcium sulfate and can be recycled for a long time, so that clean manufacturing is not only realized, Er Qiejian It is single easy.The present invention not only increase it is stanniferous decomposition slag in tin grade, and by slag most of calcium and iron convert respectively For calcium sulfate and iron hydroxide, and being recycled for a long time for hydrochloric acid solution is realized, has reached recycling and clean manufacturing Purpose.
Detailed description of the invention
The features and advantages of the present invention will be more clearly understood by referring to the accompanying drawings, and attached drawing is schematically without that should manage Solution is carries out any restrictions to the present invention, in the accompanying drawings:
Fig. 1 is a kind of flow chart of the stanniferous processing method for decomposing slag in the specific embodiment of the invention.
Specific embodiment
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, with reference to the accompanying drawing to the present invention Specific embodiment be described in detail.Many details are explained in the following description in order to fully understand this hair It is bright.But the invention can be embodied in many other ways as described herein, those skilled in the art can be not Similar improvement is done in the case where violating intension of the present invention, therefore the present invention is not limited to the specific embodiments disclosed below.
In conjunction with Fig. 1, present embodiment proposes a kind of stanniferous processing method for decomposing slag, comprising the following steps:
Step 1: washing sodium:
It is packed into suitable water in stirred tank and is warming up to 80-90 DEG C, is while stirring slowly added into stanniferous decomposition slag It sizes mixing in stirred tank, control liquid-solid ratio is 1-2:1, the hydrochloric acid that concentration is 30% is then slowly added into, by solution tune in stirred tank PH to 6.5-7.5 is saved, stirring is filtered after 0.5-1.0 hours, and filtrate is sodium chloride washing lotion of sizing mixing.
Then filter residue is washed with water, dosage is 2-3 times of filter residue weight, and water outlet sequence is pressed in washing process successively by wash water It partially collects in 2-3 wash water bucket.Then the high pressure for being 7.0-8.5MPa with operating pressure is reverse osmosis to chlorination of sizing mixing Wash water in sodium washing lotion and first wash water bucket is handled, obtain 145-155g/L containing NaCl or so strong brine and containing NaCl < The fresh water of 1.0g/L, gained fresh water continue on for being recycled next washing cycle, and gained strong brine is for being concentrated by evaporation chlorination Sodium crystal.
Step 2: acid dissolution:
The filter residue obtained after washing filtering in step 1 is stirred with dilute hydrochloric acid solution, the initial H of dilute hydrochloric acid+Concentration is 3.0mol/L-5.0mol/L, liquid-solid ratio 3-8 stir 2.0-4.0h at 80-95 DEG C in closed reactor, make reaction eventually H in acid dissolution mother liquor when only+Concentration be 0.2-1.5mol/L, acid dissolution slag and acid dissolution mother liquor, acid dissolution slag is obtained by filtration Quality can reduce to acid dissolution handle before quality 20-60%.
Step 3: precipitating arsenic removal:
It is slowly added to the H that concentration is 30% into acid dissolution mother liquor while stirring at room temperature2O2, H2O2Additional amount is pressed will Iron in solution is by Fe2+It is oxidized to Fe3+0.05-0.1 times of required theoretical amount is added, and then proceedes to use CaCO while stirring3、 CaO and Ca (OH)2One of or it is a variety of be neutralized to pH be 3.0-4.0, then proceed to stirring 10-20min after filter, obtain Arsenic scum and arsenic removal mother liquor, only small part iron is precipitated with hydroxide Iron activiation at this time, while can will be in solution Most of arsenic co-precipitation removes.
Step 4: precipitating removes iron:
Continue at room temperature side stir be slowly added into above-mentioned arsenic removal mother liquor concentration be 30% H2O2, H2O2Additional amount By by the iron in arsenic removal mother liquor all by Fe2+It is oxidized to Fe3+0.8-1.0 times of required theoretical amount is added, and then proceedes to use CaCO3 And/or Ca (OH)2It is 5.0-6.0 that the solution, which is neutralized to pH, and continues to stir 1.0-2.0h, removes solution with further precipitating In iron and filtering, obtain hydroxide scum and except iron mother liquor.
Step 5: hydrochloric acid transformation tissue culture:
While stirring to by above-mentioned precipitation and purification, treated except suitable calcium chloride is added in iron mother liquor, wait be added It is slow added into the concentrated sulfuric acid after calcium chloride dissolution, so that the calcium chloride in solution is converted into calcium sulfate precipitation and HCl solution, and normal Temperature stirs 0.5-2.0 hours under confined conditions, and wherein concentrated sulfuric acid dosage is obtained based on the HCl of 3.0mol/L-5.0mol/L by conversion It calculates and obtains the HCl densimeter of 3.0mol/L-5.0mol/L by converting for 1.0-1.1 times of required theoretical amount, calcium chloride dosage It calculates and is 1.0 times of required theoretical amount and makes excess 10-20g/L Ca in the solution after conversion2+, filtered after the completion of conversion reaction Solid calcium sulphate and conversion hydrochloric acid solution are obtained, conversion hydrochloric acid solution, which is back in step 2, to be recycled.
It preferably,, can be by as follows when containing Na > 40.0g/L in the acid dissolution mother liquor that step 2 obtains in step 3 Mode removes sodium: is neutralized after cleaning and filtering by step 3 and step 4, then by " hydrochloric acid transformation tissue culture " behaviour in step 5 CaCl is added in the requirement for making condition2And after being completely dissolved, which is concentrated by evaporation to CaCl2Concentration is 400-600g/L, cooling The sodium chloride crystal that condensing crystallizing is precipitated is filtered to remove after to 20-40 DEG C, the condensed water then recycled with evaporating concentration process And filtrate volume is supplemented to the volume before being concentrated by evaporation by tap water, the concentration of Na can be down to 1.0-10.0g/ in the solution at this time L。
For further explanation technical solution of the present invention, related embodiment is enumerated further below:
It should be understood that unless otherwise instructed, the means of use are the means of this field routine in embodiment.
Embodiment 1
Stanniferous decomposition slag after taking 500g to dry, wherein containing Sn 26%, WO30.3%, Ca 13%, Fe 18%, As 2.1%.
Step 1: washing sodium ion:
Above-mentioned stanniferous decomposition slag is mixed with 1000mL tap water and is heated to 80 DEG C after sizing mixing, is then added while stirring 30% hydrochloric acid to slurry pH be 6.5, and continue stirring 1 hour after filter, obtain wash water containing NaCl and filter cake, then every time use 250mL tap water washs filter cake, is washed three times altogether, and each wash water is individually collected.
Step 2: acid dissolution:
After stanniferous decomposition slag after originally water washing is mixed with the hydrochloric acid solution of 2000mL 4.0mol/L, at 90 DEG C It is filtered after stirring 3h in closed reactor, the dry slag of 252g is obtained after filter cake is dried, wherein containing Sn 51%, WO30.52%, Ca 5.9%, Fe 10.2%, As 0.25%.Filtering gained acid dissolution mother liquor in 25g/L containing Ca, Fe 32g/L, As 4.9g/L, HCl 1.2mol/L。
Step 3: precipitating arsenic removal:
The H of 6.0mL 30% is slowly added into 2000mL acid dissolution mother liquor obtained above while stirring2O2, then side Stirring side is slowly added to CaCO3Until pH is 3.0, then proceedes to stirring and filter after twenty minutes, As is contained in arsenic removal filtrate 0.035g/L、Fe 26g/L。
Step 4: precipitating removes iron:
The H of 45mL 30% is slowly added into above-mentioned arsenic removal filtrate while stirring2O2, it is then slowly added to Ca while stirring (OH)2Until pH is 6.0, and continues to filter after stirring 2h, obtains ferric hydroxide precipitate and except iron filtrate, remove and contain As in iron filtrate 0.001g/L、Fe 0.006g/L、Ca 48g/L。
Step 5: hydrochloric acid transformation tissue culture:
222g CaCl is added in except the filtrate after iron while stirring2, after it is completely dissolved, while stirring by 235mL 98% concentrated sulfuric acid is slowly added thereto, and is filtered after stirring 2h, is obtained calcium sulfate and the hydrochloric acid solution of 3.9mol/L, the salt after conversion Acid solution is circularly used for next acid dissolution period.
Embodiment 2
Stanniferous decomposition slag after taking 500g to dry, wherein containing Sn 12%, WO30.2%, Ca 26%, Fe 9%, As 0.6%.
Step 1: washing sodium ion:
Above-mentioned stanniferous decomposition slag is mixed with 1000mL tap water and is heated to 90 DEG C after sizing mixing, is then added while stirring 30% hydrochloric acid to slurry pH be 7.5, and continue stirring 1 hour after filter, obtain wash water containing NaCl and filter cake, then every time use 250mL tap water washs filter cake, is washed three times altogether, and each wash water is individually collected.
Step 2: acid dissolution:
After stanniferous decomposition slag after originally water washing is mixed with the hydrochloric acid solution of 3000mL 3.0mol/L, at 85 DEG C It is filtered after stirring 4h in closed reactor, the dry slag of 162g is obtained after filter cake is dried, wherein containing Sn 37%, WO30.59%, Ca 8.1%, Fe 7.7%, As 0.18%.Filtering gained acid dissolution mother liquor in 39g/L containing Ca, Fe 11g/L, As 0.9g/L, HCl 0.42mol/L。
Step 3: precipitating arsenic removal:
The H of 2.0mL 30% is slowly added into 3000mL acid dissolution mother liquor obtained above while stirring2O2, then side Stirring side is slowly added to CaCO3Until pH is 3.5, then proceedes to stirring and filters after twenty minutes, obtain arsenic removal filtrate and arsenic scum, 0.04g/L containing As, Fe 8g/L in arsenic removal filtrate.
Step 4: precipitating removes iron:
The H of 24mL 30% is slowly added into above-mentioned arsenic removal filtrate while stirring2O2, it is then slowly added to Ca while stirring (OH)2Until pH is 5.5, and continues to filter after stirring 1h, obtains ferric hydroxide precipitate and except iron filtrate, remove and contain As in iron filtrate 0.009g/L、Fe 0.008g/L、Ca 47g/L。
Step 5: hydrochloric acid transformation tissue culture:
158g CaCl is added in except the filtrate after iron while stirring2, after it is completely dissolved, while stirring by 264mL 98% concentrated sulfuric acid is slowly added thereto, and is filtered after stirring 2h, is obtained calcium sulfate and the hydrochloric acid solution of 2.8mol/L, the salt after conversion Acid solution is circularly used for next acid dissolution period.
Embodiment 3
Stanniferous decomposition slag after taking 500g to dry, wherein containing Sn 26, WO30.3%, Ca 13%, Fe 18%, As 2.1%.
By the hydrochloric acid solution after conversion by operating procedure iterative cycles processing in embodiment 1, when circular treatment to precipitating is removed Arsenic and except obtaining containing CaCl when Na accumulates to 41g/L in the acid dissolution mother liquor after iron2The acid dissolution mother liquor of 133g/L Then 2000mL adds 222g CaCl2Wherein contain CaCl afterwards2244g/L.The mother liquor is evaporated and is concentrated into volume and is 940mL wherein contains CaCl at this time2519g/L,Na 87g/L.Then the solution is cooled to 25 DEG C and continues to keep the temperature 1h so that chlorine Change sodium crystallization to be precipitated, then filter to obtain sodium chloride and except the acid dissolution mother liquor after sodium, wherein be down to 6.5g/L containing Na, with water by its Complement to 3.0g/L containing Na after 2000mL.Except the acid mother liquor after sodium is molten by the conversion operation step conversion hydrochloric acid in embodiment 1 Continue to be recycled after liquid.
Other beneficial effects include:
1, it in the present invention, is asked for what the Na that acid dissolution mother liquor is likely to occur during being recycled for a long time constantly was accumulated Topic, using the dissolubility difference of calcium chloride and sodium chloride, when Na accumulation reaches 40g/L in acid dissolution mother liquor, by neutralize with By sodium chloride, largely crystallization is removed for concentration, provides guarantee to be recycled for a long time for mother liquor.
2, in view of during " hydrochloric acid transformation tissue culture ", if need to convert, the concentration of hydrochloric acid reached is higher, and conversion is anti- Answer that difficulty is bigger and operating environment is poorer.Therefore, in the present invention, in use the hydrochloric acid (3.0-5.0mol/L) of low concentration to containing Scruff carries out acid dissolution processing, while guaranteeing to obtain ideal dissolution weight loss effect, is more advantageous to " hydrochloric acid transformation tissue culture " It carries out.
3, the present invention is applicable not only to the raising of tin grade in tungsten tin mine soda decomposition slag, can pass through hydrochloric acid for other The raw material containing stannic oxide for dissolving loss of weight is applicable.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool The purpose of the embodiment of body, it is not intended that in the limitation present invention.Each technical characteristic of embodiment described above can carry out arbitrarily Combination, for simplicity of description, it is not all possible to each technical characteristic in above-described embodiment combination be all described, so And as long as there is no contradiction in the combination of these technical features, it all should be considered as described in this specification.

Claims (10)

1. a kind of stanniferous processing method for decomposing slag, which comprises the following steps:
Step 1: acid dissolution:
By the stanniferous decomposition slag and initial H+Concentration be 3.0mol/L-5.0mol/L dilute hydrochloric acid solution in confined conditions into Row is stirred to react, and acid dissolution slag and acid dissolution mother liquor are obtained by filtration later；
Step 2: precipitating arsenic removal:
H is added into the acid dissolution mother liquor that step 1 obtains2O2, CaCO is added later3, CaO and Ca (OH)2One of or A variety of pH by the acid dissolution mother liquor are adjusted to 3.0-4.0, obtain arsenic scum and arsenic removal mother liquor；
Step 3: precipitating removes iron:
H is continuously added into the arsenic removal mother liquor that step 2 obtains2O2, CaCO is used later3And/or Ca (OH)2By the arsenic removal The pH of mother liquor is adjusted to 5.0-6.0, obtains hydroxide scum and except iron mother liquor；
Step 4: hydrochloric acid transformation tissue culture:
To step 3 obtain described in except sulfuric acid is added in iron mother liquor, make the calcium chloride in solution be converted into calcium sulfate precipitation and HCl solution.
2. the stanniferous processing method for decomposing slag according to claim 1, which is characterized in that described stanniferous in step 1 Decompose slag and the initial H+The solid-to-liquid ratio for the dilute hydrochloric acid solution that concentration is 3.0mol/L-5.0mol/L is described in 1:3-8 is carried out It is stirred to react.
3. the stanniferous processing method for decomposing slag according to claim 1, which is characterized in that in step 1, the stirring The time of reaction is 2.0-4.0h.
4. the stanniferous processing method for decomposing slag according to claim 1, which is characterized in that in step 1, at 80-95 DEG C It is stirred to react described in lower progress.
5. the stanniferous processing method for decomposing slag according to claim 1, which is characterized in that in step 2, the H2O2's Additional amount according to by the iron in the acid dissolution mother liquor by Fe2+It is oxidized to Fe3+0.05-0.1 times of required theoretical amount is added.
6. the stanniferous processing method for decomposing slag according to claim 1, which is characterized in that in step 3, the H2O2's Additional amount according to by the iron in the arsenic removal mother liquor all by Fe2+It is oxidized to Fe3+0.8-1.0 times of required theoretical amount is added.
7. the stanniferous processing method for decomposing slag according to claim 1, which is characterized in that further include washing before step 1 It washs the stanniferous sodium decomposed in slag: the stanniferous decomposition slag and water is mixed and added into the pH to 6.5- of hydrochloric acid conditioning solution 7.5, sodium chloride washing lotion is stirred to get later and except the stanniferous decomposition slag after sodium.
8. the stanniferous processing method for decomposing slag according to claim 1, which is characterized in that in step 1, when the acid It dissolves and contains Na in mother liquor+Further include the sodium ion for removing the acid dissolution mother liquor when > 40.0g/L: the acid dissolution mother liquor is steamed Hair is concentrated into CaCl2Concentration is 400-600g/L, crosses the sodium chloride crystal that condensing crystallizing is precipitated after being cooled to 20-40 DEG C and filters out It goes to obtain filtrate, the volume of the filtrate is supplemented to water the volume of the acid dissolution mother liquor before being concentrated by evaporation later.
9. the stanniferous processing method for decomposing slag according to claim 1, which is characterized in that in step 4, removed to described The sulfuric acid being added in iron mother liquor is the concentrated sulfuric acid, and the concentrated sulfuric acid dosage is calculated by the HCl that conversion obtains 3.0mol/L-5.0mol/L It and is 1.0-1.1 times of required theoretical amount.
10. the stanniferous processing method for decomposing slag according to claim 1, which is characterized in that in step 4, removed to described It is added before sulfuric acid in iron mother liquor, further includes adding calcium chloride to described remove in iron mother liquor, wherein the magnitude of recruitment of the calcium chloride The HCl of 3.0mol/L-5.0mol/L is obtained by conversion and makes excess 10-20g/L Ca in solution2+It is supplemented.
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